Resilient non-woven textile materials



Oct. 17, 1961 J. K. SUMNER ETAL RESILIENT NON-WOVEN TEXTILE MATERIALSFiled May 24, 1957 ATTO R N EY United States Patent 3,004,868 RESILIENTNON-WOVEN TEXTEE MATERIALS John K. Sumner, Plainfield, and PhilipSurowitz, Middlesex, N.J., assignors to Chicopee ManufacturingCorporation, a corporation of Massachusetts Filed May 24, 1957, Ser. No.661,280 14 Claims. (Cl. 117-140) The present invention relates to theproduction of nonwoven textile materials and more particularly to theproduction of non-woven textile materials which are resilient,dimensionally stable and relatively unaffected structurally bylaundering or dry cleaning. Another aspect of the present inventionrelates to the improved resilient, dimensionally and structurally stablenon-woven textile materials themselves and to the textile uses of thesame.

Non-woven fabrics of various types have become increasingly important inthe textile field, primarily because of their low cost of manufacture,as compared to the cost of fabrics formed by weaving or knitting spunfibers. Such non-Woven fabrics have also been found particularlysuitable for applications where launderability is not a prerequisite,especially in the case of finished products that are used once and thendiscarded, as for example, sanitary napkins, surgical dressings, casketliners, table napkins, shoe-shine cloths, dusting cloths, hand towels,diapers, drapery fabrics, and the like.

Non-woven fabrics are conventionally manufactured at the present time byseveral different methods. One of the more commonly used methodscomprises producing a more or less tenuous web of loosely associatedcarded textile fibers, followed by the lamination of several of thesecard webs together to form a somewhat more self-sustaining sheetWeighing from about 100 to about 4000 grains or more per square yard.This essentially two-dimensional web or sheet of fibers has its fiberssubstantially parallelized or oriented in the machine direction, i.e.,the direction in which the product moves continuously from thesheet-forming machine. In such a web, the degree of fiber orientationmay range from about 70% to about 90%, with the remainder of the fibersbeing non-oriented or more or less randomly disposed in overlappingintersecting arrangement.

Other methods of preparing non-woven webs of corresponding weightssuitable for conversion into fabrics applicable to the present inventioncomprise the use of fluids such as air or water to deposit the fibersand form a web wherein the fibers are in a haphazard intersectingarrangement. Such may be accomplished by processing techniques such asdescribed in US. Patents 2,676,363 and 2,676,364. Such non-woven fabricsare substantially isotropic and possess like physical properties in alldirections.

The conventional fibrous materials for such non-woven webs are usuallycellulosic and comprise any of the common textile-length or staplefibers, such as cotton, viscose or cuprammonium rayon, celluloseacetate, or mixtures thereof. These fibers vary from approximatelyone-half inch to about three inches in length, with the denier of therayon and acetate fibers being in the range of from about 1% to about15.

These non-woven webs, unfortunately, regardless of how they are formed,are not basically self-sustaining as they are intially formed by thetextile equipment and lack dimensional and structural stability. Suchinherent disadvantages have been overcome to a considerable extent bysubjecting the non-woven web to various subsequent bonding operationswherein impregnation with binder agents in overall fashion or inpatterns of spots,

"ice

lines, dots or annuli have increased the dimensional and 7 areundesirably stiff and boardy. J

Another objection to many of the prior art non-Woven fabricsmanufactured from such webs is the lack of color-. fastness and poornessof resistance to gas fading.

It is therefore a principal purpose of the present invention to providea non-woven fabric which is' not limp or flaccid but is desirablyresilient without being undesirably stiff or boardy.

It is a further principal purpose of the present invention to provide anon-woven fabric which is dimensionally and structurally stable wherebyit can be successfully and repeatedly washed or laundered Withoutfalling apart or disintegrating.

It is another principal purpose of the present invention to provide anon-woven fabric which is color-fast and non-gas fading.

Such purposes may be accomplished in these non woven webs by employingmore resilient fibers such as wool, nylon and other fibrous syntheticnon-cellulosic fibers in place of all or a part of the less resilientcellulosic fibers previously used and by coating or impregnating theresulting non-woven web with a mixture contain-. ing a thermosettingsynthetic resin and a thermoplastic tripolymeric binding agent.

The present invention wil be illustrated and described with reference tothe drawing wherein the figure is a fragmentary perspective showing of aportion of a nonwoven textile material bonded with a thermosettingsynthetic resin and a thermoplastic synthetic tripolymeric binder agent.

Although wool and nylon have been referred to in the preceding paragraphas examples of the more resilient fibers which are used in theproduction of the non-woven webs of the present invention, it is to beobserved that other fibrous synthetic materials are also of use providedthey possess more resilience than the cellulosic fibers referred toherein. Representative of such other synthetic fibrous materials arezein (Vicara), polytetrafluoroethylene (Teflon), polyester (Dacron),vinyl chloride-vinyl acetate (Vinyon), vinylidene chloride (Saran andVelon), polyethylene, and vinyl-acrylics Dynel and Vinyon N), theacrylics (Orlon, Acrylan, Creslan and Acrylast), glass (Fiberglas), andthe like. The denier of these synthetic fibers is on the order of from1% to about 15 and preferably from about 3 to about 6, with theirlengths varying from about /2 inch to about 3 inches, and preferablyfrom about 1 inch to about 2 inches.

With regard to the term resilience as used in this specification, such aterm relates to that property of a material which enables it to do workagainst restraining forces during return from a deformed state. Morespe" cifically, it is a term relating to the hand or the crease andWrinkle resistance of fabrics, and refers to their ability to recoverfrom deformation. Resilience may be fiexural, compressional, extensionalor torsional and evalulations thereof range from springy (high) to limp(low). The resilience of fibers may be evaluated in many ways, none ofwhich has been found to be very precise or highly accurate, the mostcommon being by determining their recovery and permanent set from adeforming strain.

The following table sets forth the comparative properties of variousfibers with regard to their immediate elastic recovery, their delayedrecovery after one hour and any permanent set created therein after a 5%elongation has been imposed thereon.

From Table I, it is to be noted that the less resilient cellulosicfibers fall into a group wherein the permanent 7 set after a 5% strainis 10% or more. The more resilient non-cellulosic fibers are to be notedas having permanent sets after 5% strain of 7% or less, and in mostcases, substantially zero permanent set, the latter characteristic beingparticularly applicable to the nitrogencontaining fibers such as casein,human hair, nylon and wool, possessing negligible permanent sets.

Another method has employed a 2% elongation basis wherein the values forelastic recovery are obtained at 20 C. and 65%, relative humidity, withthe rate of loading being '10 grams per denier per minute, the durationof action of load being 30 seconds and the recovery time 60 seconds.Table II sets forth the fibers tested and their elastic recoveries.

TABLE II .2 percent strain (elongation) From Table II, it is to be notedthat the less resilient cellulosic fibers fall into a group wherein thepercent recovery after a 2% strain is 94% or less of the originallength. The more resilient non-cellulosic fibers are to be noted ashaving percent recovery after a 2% strain 0E 95% or more of the originallength.

The non-woven textile webs of the present invention normally comprisemixtures of the desired fibers in a.

range of from about to about 100% by weight of the more resilientnon-cellulosic fibers and from about 75% to a negligible amount or even0% by weight of the less resilient cellulosic fibers. Within the morecommercial aspects of the present invention, the non-cellulosic fibersare present in the mixture in an amount of from about 35% to about 90%by weight and the cellulosic fibers are present in an amount of fromabout 65% to about 10% by weight. Mixtures of 50%50% proportions havebeen found to be generally desirable on an over-all basis.

cellulosic fiber may be selected for the mixture, provid- Substantiallyany more resilient non- 4 ing it creates the resiliency characteristicsdesired in the product.

Nylon is an excellent example of such a synthetic more resilientnon-cellulosic fiber and it is to be noted that the term nylon isintended to cover all polymeric polyamides produced by any of the knownprocesses known to the industry. Among the more common of thesepolyamides are nylon-6/6 (hexamethylenediaxnine-adipic acid), nylon-6/10(hexamethylenediamine-sebacic acid), nylon-6 (polycaprolactam) andnylon-.11 (Castor oil derivative, l l-amino undecanoic acid) As notedabove, the mixture of cellulosic and non-cellulosic fibers in thenon-woven web is treated with a mixture of a thermosetting syntheticresin and a thermoplastic binding agent which will be defined morespecifically in the following paragraphs.

The thermosetting synthetic resin may be selected from substantially anythermosetting resin capable of cooperating with the thermoplastic binderagent to yield the desired properties of launderability and dry cleaningresistance in the non-woven fabric. Condensation products wherein analdehyde is a reactant are particularly applicable. vFor example, thethermosetting resin may be a material selected fromthe group comprisingmelamine formaldehyde, themethylated or methyl alcohol-reacted methylolmelamines, urea-formaldehyde, phenol-formaldehyde, dicyandiamideformaldehyde, resorcinol formaldehyde, acetone-formaldehyde, phenolfurfural, etc.

The thermoplastic binding agent which is used in the mixture adheres thefibers together whereby the required dimensional and structuralstability of the non-woven fabric is obtained with the addition of thethermosetting resin. Such thermoplastic binding agents are soft andrubbery and are tripolymeric materials prepared from three monomers, onefrom each of the following groups: (1) a lower alkyl ester of acrylicacid wherein said alkyl group contains from one to four carbon atoms,such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropylacrylate, n-buty'l acrylate, iso'buty'l acrylate, see.- butyl acrylate,etc., or mixtures thereof; ,(2) an alkylene diester of an alkenoic acidwherein said akylene group contains from two to four carbon atoms, suchas ethylene diacrylate, ethylene dimethylacrylate, propylene diacrylate,propylene dimethylacrylate, etc., or mixtures thereof; and (3) analkenoic acid containing from three to five carbon atoms, such asacrylic acid, methacrylic acid, ethacrylic acid, etc. or mixturesthereof.

The proportions by weight of the individual monomers used in thepreparation of the tripolymeric binding agent may be varied according tothe requirements of the particular situation. In the case of the loweralkyl ester of acrylic acid, from about 94% to about 99.9% has beenfound satisfactory, with the more commercial ranges being from'about 97%to about 99.8%. In the case of the alkylene diester of the alkenoicacid, a range of from about 0.05% to about 2% has been foundsatisfactory, with the more commercial ranges being from about 0.1% toabout 1% by weight. In the case of the alkenoic acid, a range of fromabout 0.05% to about 4% has been found satisfactory, with the morecommercial ranges being from about 0.1% :to about 2% by weight.

Although it is preferred that the coating or impregnant mixture beapplied to the web so that it will constitute from about 20% to about byweight dry solids basis) of the weight of the finished fabric, a rangeof from about 30% to about 55% by weight is preferred in the commercialapplications of the present invention. Percentages up to 75% or more areusable where increased resistance to washability and dry cleaning isdesired, although it is to be stated that at'such higher percentagesother properties and advantages suffer.

In this mixture of thermoplastic and thermosetting materials, theproportions of these materials should be so adjusted that thethermoplastic synthetic tripolymeric binding agent is present in an.amount equal to from about 1% to about 20 times the weight of thethermosetting synthetic resin. Within the more commercial aspects of thepresent invention, however, the thermoplastic binding agent should bepresent in an amount equal to from about 1% to about 8 times the weightof the thermosetting synthetic resin, with the optimum results beingobtainable at a ratio of about 3 /2 parts of thermoplastic binding agentfor each part of thermosetting synthetic resin.

The mixture of thermoplastic and thermosetting materials may be appliedto the non-woven fabric by any means known to the industry. For example,if the thermosetting and thermoplastic materials are to be applied inthe form of an aqueous dispersion, the dry or substantially drynon-woven fabric to be impregnated may be clipped or immersed in thedispersion to provide suflicient wet pick-up of the mixture. Thewetted-out material then passes through pressure-applying rolls tosecure a substantially uniform impregnation and a controlled applicationof the desired amount of dispersion. If desired or required, thenon-woven fabric may be impregnated by any other methods known in theart. Another such method would include spraying brushing, and the like.

The wet impregnated non-woven fabric is dried and cured in the usualmanner known to the art. The drying and curing temperatures may bevaried considerably depending upon the particular thermosetting resin inthe m xture. Ordinarily, however, temperatures within the range of fromabout 250 F. to about 400 F. are employed. The impregnated fabric may beinitially dried at a relatively low temperature on the order of fromabout 200 F. to about 220 F. to remove all or a portion of the water,after which the dried or partially dried non-woven fabric is heated fora shorter period at a temperature within the range of from about 250 F.to about 400 F. to convert the thermosetting material to a substantiallywater-insoluble condition. The drying and curing operations are flexibleand may be varied to suit the available equipment. Other methodsnaturally may be employed.

The invention will be further illustrated in greater detail by thefollowing specific examples. It should be understood, however, thatalthough these examples may describe in particular detail some of themore specific features of the invention, they are given primarily forpurposes of illustration and the invention in its broader aspects is notto be construed as limited thereto.

EXADEPLE I In this example, the non-woven fabric comprises 50% nylon(3-6 denier, 2 inch length) and 50% rayon, 1V2 denier, 2 inch length.The fiber web is isotropic, with the fibers therein randomlydistributed. The fiber web has a total weight of 580 grains per squareyard.

The impregnating bath comprises the following ingreclients:

Component: Pounds Ethyl acrylate (98%), ethylene dimethylacrylate(0.4%), acrylic acid (1.6%) (46%) solids) 121 Dioctyl phthalate 16Titanium dioxide pigment 32 Melamine formaldehyde (80% solids) l8Dicyandiarnide 1 Accelerator 1 Thickener 10 Water 246 '6 When used as aninterlining for fabrics such as collars, lapels, etc., it is foundexcellent.

EXAMPLE II The procedures set forth in Example I are followedsubstantially as set forth therein except that ethylene diacrylate issubstituted for the ethylene dimethacrylate.

EXAMPLE III The procedures set forth in Example I are followedsubstantially as set forth therein except that methacrylic acid issubstituted for the acrylic acid.

EXAMPLE IV The procedures set forth in Example I are followedsubstantially as set forth therein except that butyl acrylate issubstituted for the ethyl acrylate.

EXAMPLES V-X Example 5 6 7 8 9 10 Percent TP 26 29 30 60 78 168 PercentTS 15 10 19 25 3O 31 10 9 19 21 19 176 155 313 372 740 60 97 128 148 13564 48 99 100 620 520 520 480 440 920 820 1, 060 1, 1, 400

All Weights are in grains per square yard; the percentages of the add-oningredients are based on the weight of the non-woven web.

The properties of the finished non-woven fabric are as follows:

Example 5 6 7 s 9 1o Bounce Good Good- Fair..- Good- Good- Good. CreaseResistance Good. Good. Fair.-. Good. Fair.-. Fair. softness-Stiffness.--Stifi Good- Fair.-. Good. Stiff." Good. Dry Cleaning Re- Good. GoodGood. Good- Good- Good.

sistance.

Shrinkage None- None- None- None. None. None. Color White. White White.White- White. White.

EXAMPLE XI The procedures set forth in Example I are followedsubstantially as set forth therein except that the thermosetting resinis omitted. The results are as follows:

EXAMPLE XII The procedures set forth in Example I are followedsubstantially as set forth therein with the exception that the non-wovenfabric comprises a mixture of 5 0% Dacron (ethylene glycol-terephthalicacid polyester) (3-6 denier) and 50% cellulose acetate fibers. Thefabric is useful as a resilient interlining for garments. It is capableof resisting repeated washing and dry cleaning and demonstratesexcellent dimensional and structural stability.

substantially as set forth therein with the exception that tllHOIl-WOVCHfabric comprises a mixture of 25% viscose rayon, '25 Dacron, 25 nylon (36 denier) and 25% cotton fibers. The fabric is useful as a resilientinterlining for garments. It is capable of resisting repeated washingand dry cleaning and demonstrates excellent dimensional and structuralstability.

' EXAJMPLE XV The procedures set forth in Example I are followedsubstantially as set forth therein with the execption that the non-wovenfabric comprises 100% cotton fibers.

EXAMPLES XVI-XVII In these examples, the following formulation is used:

Component: 4 Pounds TP as in Example I (46% solids) 233 Dioctylphthalate 15 Urea formaldehyde (85% solids) 33 Accelerator 1 Pigment 40vWater 68 Drying and curing is eifected at a rate of 10 yards per minuteand a. total drying time of 4 minutes. The temperature is in the rangeof 260-300 F. The web Weight is 700 grains per square yard and comprises(Example XVI) 50% 3-denier Dacron and 50% Z-denier cellulose acetate and(Example XViI) 25% 3-denier Dacron, 25 6-denier Dacron and 50% 2-deniercellulose acetate. The add-on is 450 grains per square yard. 'The totalnon-woven fabric weight is 1150 grains per square yarn.

The fabrics are evaluated with the following results:

Property Example XVI Example XVII Hand Soft, iabrlc- Soft, fabriclike.like. C0101 Stability E ce lent Good.

Good. ul 0.022. Dry Cleaning Resistance Satisfactory. Discoloration onDry Cleaning. r None. Washing Resistance Farr. Washing Resistance afterCuring Good.

Although several specific examples of the inventive concept have beendescribed, the same should not be construed as limited thereby nor tothe specific substances mentioned therein but to include various othercompounds of equivalent constitution as set forth in the claims appendedhereto. It is understood that any suitable changes, modifications andvariations may be made without departing from the spirit and scope ofthe invention.

What is claimed is:

1. A resilient non-Woven textile material comprising a fibrous webcontaining a mixture of from about 25 to about 100% by weight ofnon-cellulosic fibers and from about 75% to about by weight ofcellulosic fibers and a stabilizing and binder mixture substantiallyuniformly distributed throughout said Web comprising a thermosettingsynthetic resin and a thermoplastic synthetic tripolymeric binder agentprepared from (1) a lower alkyl ester of acrylic acid wherein said alkylgroup contains from one to four carbon atoms, (2) an alkylene di-esterof an alkenoic acid wherein said alkylene group contains from two tofour carbon atoms and (3) an alkenoic acid containing from three to fivecarbon atoms.

2; A resilient non-woven textile material as defined in claim 1 whereinthe mixture of fibers comprises from about 35% to about by weight ofnon-cellulosic fibers and from about 65% to about 10% by Weight of thecellulosic fibers.

3. A resilient non-woven textile material as defined in claim 1 whereinthe non-cellulosic fibers comprise nylon and the cellulosic fiberscomprise cotton.

4. A resilient non-Woven textile material as defined in claim 1 whereinthe non-cellulosic fibers comprise nylon and the cellulosic fiberscomprise viscose rayon.

5. A resilient non-woven textile material as defined in claim 1 whereinthe stabilizing and binder mixture constitutes from about 20 to about65% of the weight of the textile material.

6. A resilient non-Woven textile material as defined in claim 1 whereinthe thermoplastic binder agent is present in an amount equal to fromabout 1 /2 to about 2.0 times the weight of the thermosetting resin.

7. A resilient non-woven textile material comprising a fibrous webcontaining a mixture of from about 25% to about by weight ofnon-cellulosic fibers and from about 75% to about 0% by weight ofcelluiosic fibers and a stabilizing and binder mixture substantiallyuniformly distributed throughout said Web comprising a thermosettingsynthetic resin and a thermoplastic synthetic tripolyineric bindingagent prepared from (i) ethyl acrylate; (2) ethylene dimethacrylate, and(3) acrylic acid.

8. A resilient non-woven textile material comprising a fibrous webcontaining a mixture of from about 25% to about 100% by weight ofnon-cellulosic fibers and from about 75% toabout 0% by weight ofcellulosic fibers and a stabilizing and binder mixture substantiallyuniformly distributed throughout said web comprising a thermosettingsynthetic resin and a thermoplastic synthetic tripoiymeric binder agentprepared from (1) ethyl acrylate; (2) ethylene diacrylate, and (3)acrylic acid.

9. A resilient non-Woven textile material comprising a fibrous webcontaining a mixture of from about 25% to about 100% by weight ofnon-cellulosic fibers and from about 75% to about 0% by Weight ofcellulosic and a stabilizing'and binder mixture substantially uniformlydistributed throughout said web comprising a thermosetting syntheticresin and a thermoplastic synthetic tripolymeric binding agent preparedfrom (1) ethyl acrylate; (2) ethylene dimethacrylate, and (3)methacrylic acid.

10. A resilient non-woven textile material comprising a fibrous webcontaining a mixture of from about 25% to about 100% by weight ofnon-cellulosic fibers and from about 75% to about 0% by Weight ofcellulosic fibers and a stabilizing and binder m xture substantiallyuniformly distributed throughout said Web comprising a thermosettingsynthetic resin and a thermoplastic synthetic tripolymeric binding agentprepared from l) butyl acrylate; (2) ethylene dimethacrylate, and (3)acrylic acid.

11. A resilient non-woven textile material comprising a fibrous web anda stabilizing and binder mixture substantially uniformly distributedthroughout said Web comprising a thermosetting synthetic resin and athermoplastic synthetic tripolymeric binder agent prepared from: (1)about 94% to about 99.9% of a lower ailtyl ester of acrylic acidwherein. said alkyl group contains from one to four carbon atoms; (2)about 0.05% to about 2% of an alkylene di-ester of an akenoic acidwherein said alkylene group contains from two to four carbon atoms; and'(3) about 0.05% to about 4% of an alkenoic acid containing from threeto five carbon atoms, said percentages being by Weight.

. 12. A resilient non-Woven textile material comprising a fibrous webcontaining a mixture of from about 25% to about 100% of non-cellulosicfibers and from about 75% to about of cellulosic fibers and astabilizing and binder mixture substantially uniformly distributedthroughout said web comprising a thermosetting synthetic resin and athermoplastic synthetic tripolymeric binder agent prepared from: (1)about 94% to about 99.9% of a lower alkyl ester of acrylic acid whereinsaid alkyl group contains from one to four carbon atoms; (2) about 0.05%to about 2% of an alylene di-ester of an alkenoic acid wherein saidalkylene group contains from two to four carbon atoms; and (3) about0.05% to about 4% of an alkenoic acid containing from three to fivecarbon atoms, said percentages being by weight.

13. A resilient non-woven textile material comprising a fibrous web anda stabilizing and binder mixture substantially uniformly distributedthroughout said web consisting of a thermosetting synthetic resin and athermoplastic synthetic tripolyrneric binder agent prepared from: (1)about 94% to about 99.9% of a lower alkyl ester of acrylic acid whereinsaid alkyl group contains from one to four carbon atoms; (2) about 0.05%to about 2% of an alkylene di-ester of an alkenoic acid wherein saidalkylene group contains from two to four carbon atoms; and (3) about0.05% to about 4% of an alkenoic acid containing from three to fivecarbon atoms, said percentages being by weight.

14. A resilient non-woven textile material comprising a fibrous webcontaining a mixture of from about 25 to about of non-cellulosic fibersand from about 75% to about 0% of cellulosic fibers and a stabilizingand binder mixture substantially uniformly distributed throughout saidWeb consisting of a thermosetting synthetic resin and a thermoplasticsynthetic tripolymeric binder agent prepared from: (1) about 94% toabout 99.9% of a lower alkyl ester of acrylic acid wherein said alkylgroup contains from one to four carbon atoms; (2) about 0.05% to about2% of an alkylene di-ester of an alkenoic acid wherein said alkylenegroup contains from two to four carbon atoms; and (3) about 0.05% toabout 4% of an alkenoic acid containing from three to five carbon atoms,said percentages being by weight.

References Cited in the file of this patent UNITED STATES PATENTS2,340,111 DtAlelio Jan. 25, 1944 2,343,095 Smith Feb. 29, 1944 2,464,826Neher et al Mar. 22, 1949 2,698,574 Dougherty et al. Jan. 4, 19552,778,283 Bettoli et a1. Ian. 22, 1957 2,782,130 Ness et a1 Feb. 19,1957 2,823,142 Sumner et a1. Feb. 11, 1958 2,865,783 Henderson et al.Dec. 23, -8

1. A RESILIENT NON-WOVEN TEXTILE MATERIAL COMPRISING A FIBROUS WEBCONTAINING A MIXTURE OF FROM ABOUT 25% TO ABOUT 100% BY WEIGHT OFNON-CELULLOSIC FIBERS AND FROM ABOUT 75% TO ABOUT 0% BY WEIGHT OFCELLULOSIC FIBERS AND A STABILIZING AND BINDER MIXTURE SUBSTANTIALLYUNIFORMLY DISTRIBUTED THROUTHOUT SAID WEB COMPRISING A THERMOSETTINGSYNTHETIC RESIN AND A THERMOPLASTIC SYNTHETIC TRIPOLYMERIC BINDER AGENTPREPARE FROM (1) A LOWER ALKYL ESTER OF ACRYLIC ACID WHEREIN SAID ALKYLGROUP CONTAINS FROM ONE TO FOUR CARBON ATOMS, (2) AN ALKYLENE DI-ESTEROF AN ALKENOIC ACID WHEREIN SAID ALKYLENE GROUP CONTAINS FROM TWO TOFOUR CARBON ATOMS AND (3) AN ALKENOIC ACID CONTAINING FROM THREE TO FIVECARBON ATOMS.